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Design of Photothermal Covalent Organic Frameworks by Radical Immobilization

CCS Chemistry 2022年第8期4卷 2842-2853页

作者： Xiaohui Tang Zhongxin Chen Qing Xu Yan Su Hong Xu satoshi horike Huanhuan Zhang Yuan Li Cheng Gu State Key Laboratory of Luminescent Materials and Devices Institute of Polymer Optoelectronic Materials and DevicesSouth China University of TechnologyGuangzhou 510640 CAS Key Laboratory of Low-Carbon Conversion Science and Engineering Shanghai Advanced Research Institute(SARI)Chinese Academy of Sciences(CAS)Shanghai 201210 Institute of Nuclear and New Energy Technology Tsinghua UniversityBeijing 100084 Institute for Integrated Cell-Material Sciences Institute for Advanced StudyKyoto UniversityYoshidaSakyo-kuKyoto 606-8501 Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates South China University of TechnologyGuangzhou 510640

Covalent organic frameworks(COFs)characterized by structural diversity,face-to-face stacking and open channels exhibit unique advantages as photothermal materials but have rarely been applied in solar-driven water evaporation due to complicated framework design,tedious synthesis,and low solar-to-vapor efficiency.Herein,we report a materials design strategy to produce efficient and robust photothermal COF by anchoring nonemissive radicals to the pore surface by a[2+2]cycloaddition–retroelectrocyclization reaction.

关键词： covalent organic frameworks radicals photothermal conversion water evaporation

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Glassy State of Metal-Organic Framework for Ion Conductivity

Glassy State of Metal-Organic Framework for Ion Conductivity

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中国化学会第十五届固态化学与无机合成学术会议

作者： satoshi horike Kyoto University Institute for Advanced StudyInstitute for Integrated Cell-Material Sciences AIST-Kyoto University Chemical Energy Materials Open Innovation Laboratory

Solid-state ion conductors are significant class of materials for battery, fuel cell, electrocatalysis, and artificial ion channel, etc. Not only to achieve high ion conductivity, the control of temperature region of ion conduction, or switching of ion conduction by external stimuli is important challenge for application. Control of mechanical property and electrochemical stability are also required for solid-state ion conductive materials. Coordination Polymer（CP） or Metal Organic Framework（MOF） constructed from metal ions and bridging molecular ligands are promising materials for solid-state ion conductors.[1] Some CP/MOF crystals offer anhydrous H+ conductivity over 10-3 S cm-1 at 120 °C.[2] Recently we have focused on the glassy state of CP/MOF crystals（Fig. 1）. Glassy state is in general isotropic and dynamic compared with the crystalline state which will be advantageous for ion conductivity. We found several CP/MOF crystals melt as heating, and accordingly form glassy state.[3] Some CP/MOF crystals directly transform to glassy state by mechanical milling.[4] In both cases, we found significant improvement of H+ conductivity compared with the crystalline state. X-ray total scattering and solidstate NMR experiments suggest the glassy states retain the identical coordination geometry around the metal ions, and even network structures. Design of ion conduction pathway in CP/MOFs under crystal/glass states will be discussed.

关键词： Proton conductivity Glass Metal-organic frameworks Solid-state NMR Phase transition

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